Vat dyes of the thioindigo series



faiimtea Jan ii, 192$.

om'ran STATE S x 1,558,458 PATENT oF'FwE.

v 1 v WILLJKIRII JOYCE, OF NEWARK, NEW JERSEY, ASE- IGHOB, TO THECHEMICAL FOUNDATION, INCOR?ORATED, OF NEW YORK, N. 757-, .8. CORPGRATIDNF DELA WARE.

VAT DYES OF THE THIOINDZGQ SERIES.

1% Drawing. Application filed January To oil wimm "it FYI/(Ly lgionce'r-nr I it known that I, Am XVILLARD JOYCE, (1 men of the UnitedStates residing at NP," FLT, in. the county of and Siam of F- by haveinvented certain new and u. i l ipzi'wenionts in Vat, Dyes of the'luiioiniiigo Sories, of whioh the follow ing is a full, clear, and amokdescription,- SLiCil as will 01 ole others Hod in "the art to which itappertains to make and use the some,

' This invention relates to file i'nanufaoim'o of wit dyes of thethioindigo series and inoiu s correlated improvements and dis iesrelative to the production of oi? dyes.

An object of the invention is to provide 2: process for the manufactureof vat dyes of the; thioindigo series whereby the some may be readilynmunfactured in an Economical HDUZIICT.

hiother obj'aot of the invention is to pro- U "\Jisiib are of Value inthe dye-- in; and priming of cotton and silk.

knothe (-izieot of the invention is to pro- ;n will produce edoiuisivred shades w ge".

i. mom oijeot of the invention is to H103 tide va a dyes which possessthe property of 1 w; to .ilgiilt shim-me, \"msinng alkalzes w oi theinvei' Lion win in m will 111 1321i appear hereinmrr'ordingly comprisesthe ation and order-0f o a )S with msygect to each products possessings, anti the relation. of "*ipiif'iud in ii;

and the inveniior stops a: i of $101 of tho invention, a ibderi i-fichior'8-oxy-1-h1ow 1.. osizer derivati'iies having substiment groups inthe 2-) position which react in a 28, 1925- Serial No. 5,53'34.

similar manna? to the koizo'group, may be condensed with a3--oxy-l-ih1onaphtheno do r1\ 'at1ve ha *mg subsiituszit groups in thebenzene ring such an a3 yi-oxy group, and

an alkyl-oxy and-a haiogelm This reaction.

yields new thioindigo dyes which dya animal and vegetabie fibres from'12. ire guifiio vat orange-red to oiuisia "oci ii-mks. Some of tho m ybe for. i221 halo-- genateii, as bromimzioci or olmorinated, therebyyieiding' products which are blue! in shade than the lmif-ialogenatsd(Eye.

The roaotio 2112: to married 011%,- i'i nyheat the derivnl; es abovementioned together n a uiiaa bie recepocloa This roaof'on mag oacooznplishod in tho of a "vent in the presence of coml ion agent Whenempioying ssh-ant, utiiizw tion may be modsof glacial benzene, toluene,niti-obenzonei, when employing a: concisnsing tic may be made of zincGIHOIIKLQ anhydrizlo minors acids.

The Vii-i1 produoeci when in form of a dry powder are of an orzux owedto a hriowiir'ted or; in Watar, alcohoi and @931 Th2 issoi'v-s innitrobenzene with the formation of an orange-Ted to a bluish-redsolution and in concentrated sulphuric acid with the formation of agreen. solution, Further; they dissolve readily in alkaline.izydrosulfite solutions forming Yellow vats from which. cotton and silkare oiyeoiorangwrod to bluish red 5 sides, The dyes produced. posseosexcellent fastness to light cl iiorine, W fishing, alkalies and acids'.

As iiiustrative embodiments of a manner in which the -on be oarrieziinto pradaioo and. U1, iorofiuots produced, the following exm'npiq, I;,g1*e.:o1zted: The yarts are by weigslt,

Emmi/pie. 1.

pa is of mnthylfi-oh1or-2.3 dike'to- .ihydzo l-thionaphtoenofi'oximezare dissolved in 250 parts o Racial 2.129% is acid with the aid of heat.iaiiie-ii ccmpiotely dissoived a solution of part5 of i-biC lIl-SfithOX)S-oxydihionapbthono, in G paits oi glacial acetic acid aro guicied andtho mizzturoheatod at 100 f). fol-l two 11 11 s or untii 'the'formationof the new dye is complete. After 0001- ing to room tomperatmo, the dyewhich separates is fi'iiaexd, Washed ami dried. It

constitutes e bllCk-TQd,POWCiQl' which dissolves inconcentmtecl sulfuricacid to it green solution. With hydrosulfite and caustic socizi ityields a yellow vat from which cotton is dyed a clear bluish-red, afterbeing sozipetl.

Example 2.

33.9 parts of p-dimethyleminoe-inethyL J6-chlor-2.3-diketo-dihydro-1=thionaphthene- 2-anil are dissolved in 500parts of glacial acetic ecitl by heating to boiling under re flux for tominutes. A solution of 19.5 arts of 6-ethoxy-3wx -1-tliionaphthene in200 parts of glacial acetic acid is now added and the mixture boiled fortwo hours or until the condensation is compicteii. After cooling to roomtemperature, the dye is filtered, washed and drietl. It constitutes a 29bright orange-red powder, soluble in con ,centrstecl sulfuric 'acid witha green color. it is easily soluble in the alkaline hydrosulfite vatfront which cotton is dyed o bright oil-angered, possessing excellentfastness to light, chlorine and woshin V ihe mother liquors containp-amino-dimethyl-aniline, a useful by-procluct, which may be recoveredwithout clifiiculty from the .iiquor.

' Example 3.

parts or p-rlimethylcmino-6-etho2zy- 2.3-clileto'-(lihydro-l-thionaphthene 2 soil contieiisec with 20.0 parts ofle-methyl- 6chlor-3-oxy l thionziphthene under the i he 35 conditionsdescribed in Example 2.

e termed is identical with that ootemetl 1r. EXRIIlPlG 2.

Example 1;.

4% 37.6 ports of the dye formed. in either of the foregoing Examples 2or 3 are dissolved in 1000 arts of concentrated sulfuric acid by the sidof slight warming and stirring. hem the dye is ciissolved, the solutionis cooled to room temperature and part of iodine crystals added. Then,during the course of about two hours, 16.0 parts of liquici bromine arestltleti. The bromine tion proceeds smoothly at room temperature and maybe completed without warming.

When free bromine ceii no longer be rletected, the mixture is pouredinto a large volume of ice and water, whereby the new monobrominatecldye separates in hright red. flocks, which are filtered, washed, anddried. It consists of. s. bright red powder, yielding a. green solutionin concentrated sulfuric acid. Cotton is dyed from the "Z vet a brighthiuishlight, chlorine used for the monobroiniimtctl (lye. HOW- ever, tocomplete the bromineticn, it may he necessary to Warm to e tempcrotureof about 4550 C. toward the end of the reaction.

The dibrominateti dye is bluer in shade than the monobrommatecl product,out in other A current of chlorine is into sulfuric acid solution. oithe dye as prepared in the foregoing; simple 41'! 1I2.'Gil l1 ports havebeen fillOWCtl to react. The new mono hlorinateci (lye can he isolate-clin. manner similar to tile hrominuted precincts. Double the quantity ofchlorine gives e dichloriuetecl product with similar properties to themono-chlorinated (lye.

The chlorinstetlproclucts are not as loiue in shade as the hrorninateddyes, hut in comparison with theunhologenatetl dye, they have increaseclfastness to light, chlorine and washing.

l'nthe production of chlorinated products other solvents may he usedsuch [is nitroheuzol, chlorhenzols, etc; iilrewise, other chlorinetingin ents, as sulfur chloride, sulfuryl chloride, etc.

As iliustrotive of other derivatives of mcthyi-S-chlr3-o;ry-i-thionophthene tl 4-. ethyl- 6-chlor-2.3- iiireto-ciihylro-1-chic nephthene which may he used, reference is made to p-(limethylamiuo--methyl-6-chlor 2.3 dikcto-dihyclro-l-thionaphthenc- 2 mili-methyl-G-chlorm ilikcto-clihyiro-1 thio naphthene-Q-orrime cliketo y athe benzene ring which may he advantageously employeii, reference ismzule to cthozy-ii-oxy-l thionuphthcne or ow herein xiescribe is and.4-methexy-3-oxy-l-thionaphtheme.

While the eeestiwtien of the vat dyes not riefinitely knewn, it isbelieved thee their constitution is most p'rpbabiy represented by thefollowing gem eral structural formula:

difliktfifi an aryi greup which min 5; a suhstiwentgroup, an. aikyfiirxe rand bmmine,

in sem inain 1110c! ezu bexiy the inve. ti xii depar'tie e'fienfied$1.13!: all e scepe, tanned. m

ended tq ewe:- ail Hires: ef the i we azui. all

inventi e while, axe e 0f Zanggmzge, migh' said in fan i'be-fi my,inventien, what 31 we} desire to by Letters 4. A process for themanufacture of vat dyes of the fluemdxgo serms wine-h com prisescondensing eE-derimtive of e-mei-h L 7, 1; :1 n t--e]'u0r-i-exy'Ltnwnaphmene Wlth e de meme. e

5; As: new n-m e, the izereilx (.?.e:-ieribed m dyes Hf the theindigeseries, having m st' probably the foflewing genera: structuralfermelewherein R "221 am am my! gmug, containing as substituent aneikyi-eezy gmup, being in dry estate red pewdem, ineehlble in waereieehel and mixer, eelnble in nitrabe zyzene with an erezxgere left,eelubie in concentrated suifuric acid w uh a gl'een Q0102 fanningwithii'a 37' E315 h ires iite 50hr tfion. yelie item which a ism amt"map eeneeam Y ggeap e a a whezi. in. 1a mg; as sash. he

smfite enhzti mei and red shades, W1 and washing.

'2'. As a new ,proue: the herein; deseribe'l thieindige ste eye ofeenst' itufienai muzzle:

v. 12511- eight chlorine derived by the eoudezz satien cf 4-1119,"31:71-6- cider-2.3 dlkete ehhydro 1 thloraphthene and its iZ-ketoequivaients with fieishoxy-3.-

oxy-Lthionephthene, bein in a dry state an orange-red powder,:inseluTvIe in Water, alcohol and ether, amiable in nitrobenzene with:12. omngereai c010? and. giei-iing in ewe-e21 Med sulfuric excl e fhefeiiewing prc-bable I grew SOEUMOEIE term yellmv vafiirom wliuh aninuland vegsiable fibres dyer brig t orange-red shades; lust ilghi, chlog'memm W As a new product, i lhlomdlgo Yuk dye of sine constliutscnalformula:

D ne nerem described foilowmg probable waived by 11116 brombmtion sf the60116.91;- sntmn pi'aduct {mm i' nwtiiyL-Sahlm ffi-

